Sulphonated higher unsaturated carboxylic esters of polyhydroxy substances



sulphonation primarily to designate theaddi-Jv l atented Jan. 28, 1936" SULPHONATED HIGHER UNSATURATED CARBOXYLIC ESTEBS OF POLYHY- DROXY SUBSTANCES Benjamin R. Harris, Chicago, Ill.

No Drawing. Application November 16, 1929, a Serial No. 407,796

Claims. 01. zoo-100i My invention relates to a new class of chemical products and processes for making same.

These'substances have many advantages in the arts and many uses, which will be described laterj The materials I have discovered are fatty compounds with an oleaginous radical or group and with a sulphuric acid radical or radicals associated with it, My products are solid at ordinary temperatures and it is this property which, among others, distinguishes them from and endows.-

them with important advantages over the sulphonated oils of commerce known heretofore.

Another departure which 'I make from the art of sulphonation as practiced heretofore is that the fatty material which I subject to the action of the sulphuric acid, chlorsulphonic acid or other sulphonating agent, isgenerally speaking relatively less unsaturated than the fatty oils used heretofore. The proportion of carbon to carbon double bonds per unit weight of material is relj ativelylessthan in the fatty oils usedheretofore.

Furthermore, as a consequence of this, my .su1-' phonated products, may be prepared, if desired,

. to contain relatively smaller proportions of combined sulphuric'acid than are present in the sulphonated oils made heretofore.

Throughout this application I use the term tion of sulphuric acid or its equivalents to a carbon to carbon double bond,

In a co-pending application, Serial No. 475,622, filed August 15, 1930, now Patent No. 1,917,250 I ,have described some of the methods I have used 'in the manufacture of such substances and their use in connection with the reduction of spattering in 'oleomargarine and like products duringfrying.

In the presentspecification I describe more 7 fully the nature of these substances, various temperatures such as olive oil or castor oil, were methods -for their manufacture and pointv out their uses in the arts.

In the art known heretofore as the sulphonation of oils, oils which are liquidat ordinary treated with sulphuric acid to produce materials which, are liquid at ordinary temperatures, in

which the sulphuric acid radical is added to a double bond producing acid sulphates in'solublein I water, together with a not inconsiderable proportion of by-products such as free fatty. acids.

In order to make them Water soluble,- these products are neutralized with alkali such as sodium ammonium, potassium hydroxide, carbonate or bicarbonate or the like or. other alkaline agents.

Unsaturated liquid fatty acid such as oleic acid or fatty acids of castor oil, which are liqu'id at ordinary temperatures, were also sulphonated in the same manner, producing substances which are insoluble in water but which .become water soluble after being neutralized with an alkali.

An object of my present invention is to producederivatives of carboxylic esters whichcontain hydrophylic radical such as a sulphate group and which are solid at ordinary tempera- 10 tures. They also have certain distinct physicochemical properties in that they are substantially insoluble in w iager but are colloidally dis: persible therein. ey also have the property of imbibing large amounts of water to an extent up to threeto four times their own weight.

An example of one way in which my invention may be carried out is as follows; lollpounds of oleo stearine, of the commercial kind obtainable from packing houses, are treated with 200 pounds of concentrated sulphuric acid, (sp. g. 1.84) preferably controlling the temperature so that it does not rise substantially above 38 or 40 C., by maccrating, kneading or grinding the sulphuric. acid with the oleo stearine and allowing the mixture to run to completion, generally from twelve to eighteen hours. A

The mixture is then mixed with about 500 gallons vof cold water by maceration for the purpose hf dispersing same. -Thirty pounds of common salt are their dissolved in this mixture which is then allowed to remain at rest. The sulphonated carboxylic esters, together with a proportion of other reaction by-products, come to the top in the form of small curdy particles.

This product is washed several times with water, followed by saltingout as above, so as to eliminate the free, uncombined sulphuric acid.

The washing out of the free uncombined sulphuric acid may be facilitated by dispersing the sulphonated material in warm water, say at- 60 to C. This gives a fine milky emulsion.

A'propo'rtion of salt is now dissolved in this emulsion, 1%% or more, andthe sulphonated'material floats to the surface and forms, in many cases,

sulphonated.material may .now again be dispersed in warm water and the procedure repeated until the free, uncombined sulphuric acid has been sufncien'tly washed out.

Finally the mixture is allowed to cool and the product is skimmed from thetop. Thisproduct may contain imbibed water. More water may 55' v 'to stand for a suflicient time toallow the reactiona clear. fat layer; The brine is drawn off; The

, 0d of manufacturing the solid sulphonated escontaining such double bonds in proportions smaller than present in the oils used heretofore for sulphonation.

I do notv wish to limit myself to the above methters. I can use varying amounts of sulphuric acid, but the amount of sulphuric acid/must be sufficient to produce the desired sulphonation. In place of sulphuric acid of sp. g. 1.84, I can use fuming sulphuric acid, chlorsulphonic acid or other sulphonating agents. A

The application of my invention is by no means limited to triglycerides as'I have obtained good products by treating other esters which are solid at ordinary temperatures and which contain carbon to carbon double bonds capable of adding on the elements of sulphuric acid, Examples of such esters are: cetyl glyceryl ether mono oleate H, 0ll-CnHai mono-oleyl-tri-stearyl diglycerol 0 I H: O-g-CaoH|o tri-stearyl castor oil cetyl olegate and other esters such as suitable esters of glucose, sucrose, mannitol, sorbitol, diethylene glycol, etc. a

I prepare these products by the same methods used in sulphonating oleo stearine. For example, pounds of one of the esters described above are treated with 200 pounds of concentrated sulphuric acid (sp. g. 1184), preferably controlling the temperature so that it does not rise substantially above 38 to 40C., by macerating, kneading, or grinding the sulphuric acid with the product and allowing the mixture to stand for a sufllcient time to allow the reaction to run to completion, generally from twelve to eighteen hours.

The mixture is then mixed with about 500 2,029,168 be incorporated in it if it is desired to bring it pose of dispersing same. Thirty pounds of common salt are then dissolved in this mixture which is then allowed to remain at rest. The sulphonated carboxylic esters, together with a proportion of other reaction by-products, come to the top in the form of small curdy particles.

This product is washed several times with water, followed by salting out as above, so as to eliminate the free, uncombined sulphuric acid.

The'washing out of the free uncombined sulphuric acid may be facilitated by dispersing the .sulphonated material in warm water, say at 60 to 70 C. This gives a fine milky emulsion. A proportion of salt is now dissolved in this emulsion, 1 or. more and the sulphonated material floats to the surface and forms, in many cases, a clear fatty layer. The brine is drawn oil. The sulphonated material may now again be dispersed in warm water and the procedure repeated until the free, uncombined sulphuric acid has been-sutficiently washed out.

Finally the mixture is allowed to cool and the product is skimmed from the top. This product may contain imbided water. More water may be incorporated in it if it is desired to bring it into a pasty consistency.

In sulphonating these products, I do not limit myself to the above described method. I may use various amounts of sulphuric acid, but the amount should be suflicient to sulphonate the product at the double bonds in order to produce the result desired. In place, of sulphuric acid (sp. g. 1.84), I may use fuming sulphuric acid, chlorsulphonic acid or other sulphonat ing agents.

The term sulphonation is employed to define a mechanism wherein a sulphate group is attached at the, carbon to carbon double bonds.

In general, my sulphonated" products are superior to the sulphonated oils heretofore known in commerce principally by virtue of their property of being solid at ordinary temperatures. The uses of the sulphonated-oi1s known heretofore are circumscribed by the fact that they are liquid at ordinary temperatures. This is a very important-difierence for it'makes possible a wide field of usefulness for my products in the textile, paper, pharmaceutical, soap, cosmetic, dyeing, food-and other industries as wetting, penetrating, detergent, foaming, lubricating agents, etc.

My sulphonated" products may be used singly or as mixtures of several of my sulphonated products. Also,.they may be compounded with soaps, sulphonated soaps, .sulphonated" oils, perfuming agents, dyes, medicating agents, abrasives or other materials, with which it may be desired to have them coact and such mixtures may be marketed as bars, sticks, crayons. pomades, powers, etc.

I am aware that wool fat, wool grease, or lanolin (which words are used almost synonymously) have been sulphonated to produce a water dispersible solid product, It is not my intention to claim substances of this kind as my invention is directed to sulphonated carboxylic esters of polyhydroxy compounds such as glycols,

glycerine, and sugars. Many examples of these compounds are given in the preceding paragraphs. Although wool fat is called a fat, in a strict technical sense it is not a fat, but in some cases is composed almost entirely of cholesterol and cholesterol derivatives. The glycerides or fatty substances used in my invention, on the contrary. will be found to contain approximate- 5 phate group attached to a carbon at a double bond of the unsaturated fatty acid.

2. The method of forming a new chemical compound which comprises intimately mixing a higher unsaturated fatty acid ester of a sugar, which ester is solid at normal temperatures, with'a sulphonating agent, allowing the mixture to stand until the sulphonating action is substantially completed, and finally neutralizing and washing the resulting compound until the excess sul-' phonating agentis removed.

3. A sulphonated derivative of saturated aliphatic carboxylic acid ester of a water soluble carbohydrate, the ester being solid at room temperatures, the sulphate group being ,attached to carbon at a double bond of the acid radical. r

4. A sulphonated derivative of a higher unsaturated aliphatic carboxylic acid ester of glupose, the ester being solid at room temperatures, the sulphate group being attached to carbon at a double bond of the acid radical.

5. A derivative of a higher unsaturated aliphatic carboxylic acid ester of a sugar, the ester being solid at ordinary room temperatures, and having a sulphate group attached to, a carbon at a double bond of the unsaturated aliphatic carboxylic acid.

6. A derivative of an unsaturated higher organic carboxylic acid ester 'of a sugar, the ester being solid. at ordinary room temperatures, and having .a sulphate group attached to a carbon at a double bond of the unsaturated organic carboxylic acid. v y

7. The method of forming a new chemical compound which comprises intimately mixingja highr unsaturated aliphatic carboxylicacid ester of a sugar, which ester is solid at normal temperatures, withv a sulphonating agent, allowing the mixture to stand until the sulphonating actionis substantially completed, and finally neutralizing and washing the resulting compound until the excess sulphonating agent-is removed. 8. The method of forming a new chemical coma higher unpound which comprises intimately mixing a higher unsaturated organic carboxylic acid ester of a sugar, which ester is solid at normal temperatures, with a sulphonating agent, allowing the mixture to stand until the sulphonating action is substantially completed, and finally neutralizing and washing the resulting compound until the excess sulphonating agent is removed.

9. A sulphonated derivative of a higher unsaturated organic carboxylic acid ester of a water soluble carbohydrate, the ester beirig solid at room temperatures, the sulphate group being attached to carbon at a double bond of the acid radical.

10. A sulphonated derivative of a higher unsaturated fatty acid ester of a water soluble carbohydrate, the ester being solid at room temperatures, the sulphate group being attached to carbon at a doubleu bond of the acid radical.

. 11. A sulphonated d erivative'of a higher unsaturated organic carboxylic acid ester of glucose, the ester being solid at room temperature,

the sulphate groupbeing attached to carbon at a double bond of the acid radical.

12. A sulphonated derivative of a higher unsaturated fatty acid ester of glucose, the ester being solid at room temperature, the sulphate group being attached to carbon at a double bond of the acid radical.

13 A sulphonated derivativeof a higher unsaturated organic carboxylic acid ester of a polyhydroxy alcohol, the ester being solid at room temperatures, the carbon residue or said polyhydroxy substance containing more than three carbon atoms, the sulphate group being attached to carbon at a vdouble bond of the acid radical.

14.'A sulphonated derivative of a higher un-; saturated aliphatic carboxylic acid ester of a polyhydroxy alcohol, the ester being solid at room temperatures, the carbonresidue of said polyhydroxy substance containing more than three carbon atoms, the sulphate group being attached to carbon at a double bond, of the acid radical.

l5. A.sulph nated derivative of a higher unsaturated fatty acid ester of a polyhydroxy alcohol, the ester being solid at room temperatures, the carbon residue of said polyhydroxy substance containing more than three carbon atoms, the sulphate group being attached to carbonat a double bond of the acid radical.

BENJAMIN R. HARRIS. 

